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HUMID AIR
Models and Background
Disclaimer
This document reports results of our own work, based on results published by others, in the open literature.
The author, his firm, and his associates assume no responsibility whatsoever regarding whatever consequences,
direct or implied, that may result from their use or misuse.
In no circumstances shall the author, his firm, and his associates be made liable for any losses of profit, or other
commercial damages, including, but not limited, to special, incidental, consequential or other damages.
Fluid Properties
The models of the components used in HVAC equipment and plants require the knowledge
of a large number of thermodynamic and transport properties of the fluids they handle. In a
model conceived for design purposes those properties must be calculated for real fluids, as
stressed by Black (1986). The fluids used may be undergoing a cyclic process, such as the
operating fluid in a chiller or heat pump, or may be totally or partially recirculated as the source
and sink fluids, mostly humid air, water or a brine. The thermodynamic and transport properties
of operating fluids are required for the liquid and the vapour phases, and for the two-phase
liquid-vapour region as well. Water and brine properties are mostly necessary for the liquid
phase, although solid water (frost and ice) properties may as well be required when the source
fluid is atmospheric air, or an ice producing heat pump. This document describes the equations
necessary for the calculation of the thermophysical (thermodynamic + transport) properties of
moist air in a coherent manner, and gives the necessary parameters.
[1]
0.349568x102
0.125975x104
-0.668772x104
-0.190905x106
-0.210141x107
0.632467x108
0.924746x108
[2]
0.70x10-8
0.104x10-14
-0.147184x10-8
-0.335297x10-17
1734.29
3645.09
[3]
Xa and Xw are the molar concentrations of air and water vapour in the mixture, respectively.
Baw, Caaw, and Caww are the second and third cross-virial coefficients of the air-water vapour
mixture, respectively. They are calculated from
[4]
with
i
0.32366097x102
0.482737x103
-0.10728876x102
-0.141138x105
0.105678x106
0.347802x104
-0.1244535x107
-0.656394x108
-0.383383x106
0.0
0.299444x1011
0.33406x108
-0.2348789x1010
-0.319317x1013
-1.0x106
[6]
with
i
0.63290874x101
-0.5008x10-2
0.28709015x102
0.32491829x102
0.26431805x10-2
0.65576345x10-2
-0.10405863x10-4
-0.26442147x10-4
0.18660410x10-7
0.517517889x10-7
-0.9784331x10-11
-0.31541624x10-10
The reference state currently adopted for the computation of the enthalpy of humid air is
0 EC, at normal sea level pressure (p = 101325.16 Pa), and null water vapour content, with the
molecular enthalpy set to zero (0.0) at that point. The integration constant hG 'a is -7914.1982
J/mol. Choosing the reference state for water as the liquid state at the triple point, with null
enthalpy, leads to the integration constant hG 'w = 35994.17 J/mol. The derivatives of the cross
virial coefficients Bm and Cm with respect to temperature are from their respective equations
given before.
[7]
0.34373874x102
0.2196603x101
0.52863609x10-2
0.19743819x10-1
-0.15608795x10-4
-0.70128225x10-4
0.24880547x10-7
0.14866252x10-6
-0.12230416x10-10
-0.14524437x10-9
0.28709015x102
0.55663583x10-13
0.32284652x102
The integration constants for the reference states as given above, are
Specific Volume, Enthalpy and Entropy per Unit mass of Dry Air
The conversion of the volume, enthalpy and entropy from a molar basis to massic
quantities, per unit mass of dry air, is done by dividing the molar values by the actual mass of
dry air in the mole of mixture:
[8]
where psv is the saturation pressure of water vapour over liquid or solid water. p is the total
pressure of the mixture. f is a dimensionless quantity introduced by Goff (1949), the so-called
enhancement factor. It is a function of pressure and temperature, and accounts for the nonideal
behaviour of the mixture in the saturated state. The saturation pressure, [kPa], of water over
solid and liquid water is given by (Saul and Wagner 1987),
[10]
[11]
22 064
Tcr,H2O [K ] =
647.14
213.15 K # T # 273.16 K
273.16 K # T # 647.14 K
A1
2.442 663
-7.858 230
A2
-11.413 077
1.839 910
A3
-15.109 346
-11.781 100
A4
1.119 193
22.670 500
A5
18.159 568
-15.939 300
A6
-6.138 264
1.775 160
The equation for saturation over liquid water also reproduces well measurements over
subcooled water down to 223.15 K.
[12]
[13]
-0.2403360201x104
0.1070003x10-2
-0.140758895x101
-0.249936x10-7
0.1068287657
0.371611x10-9
-0.2914492351x10-3
0.373497936x10-6
-0.21203787x10-9
-0.3424442728x101
0.1619785x10-1
is the isothermal compressibility of the condensed phase. Kell (1975) proposes the
following equation for its calculation over liquid:
[15]
0 < t # 100 EC
0.5088496x102
0.50884917x102
0.6163813
0.62590623
0.1459187x10-2
0.13848668x10-2
0.2008438x10-4
0.21603427x10-4
-0.5847727x10-7
-0.72087667x10-7
0.4104110x10-9
0.46545054x10-9
0.1967348x10-1
0.19859983x10-1
Hyland and Wexler (1983) state that the above Eq. [15] may be used for temperatures up
to 200 EC "with little degradation in accuracy".
a is the Henry's law constant for air. This constant relates the mole fraction of a gas
dissolved in the condensed phase to its partial pressure in the gaseous phase. The Henry's law
is expressed as
[17]
where
pGG
XGL
a is related to the individual values for oxygen, O, and for nitrogen, N, over water,
assuming the air to be composed of just these two main components.
[18]
-1.142
2.846
-2.486
0.9761
-0.2001
is defined as
[20]
where Tc = 647.25 K is the critical temperature of water. The other values are given for
oxygen and nitrogen in the following table.
1/Tmax
max
[K-1]
[atm/mol fraction]
oxygen
2.73x10-3
7.08x104
844.3/T - 1.305
nitrogen
2.80x10-3
12.39x104
797.2/T - 1.232
substance
For a given temperature T, is calculated and used in the equation for to determine its
value for oxygen and nitrogen. This permits the calculation of a. For temperatures lower than
273.15 K, the value 1/a is assumed null. Himmelblau (1960) claims that errors in N and O do
not exceed 3% for 283.15 K < T < 433.15 K, and 15.1% for 273.15 K < T < 647.0 K.
The condensed phase is assumed to be solid water if T is smaller than the melting
temperature of ice, TM, which is given by Zemansky and Dittman (1981) as
[21]
where TTP is the triple point temperature of water, 273.16 K, and pTP is the triple point
pressure of water 0.006112 bar.
The equation for the enhancement factor f, may now be solved by iteration on both Xas and
f, up to an accuracy 1 part in 106 or better for f.
The humidity ratio, , is the amount of water vapour (mass) per unit mass of dry air in the
mixture. Mathematically,
[22]
where Mw and Ma are the molecular masses of water and air, respectively.
The actual mole fraction of water vapour in the mixture, Xw, and of air, Xa, are respectively
[23]
[24]
Dew-Point Temperature
The dew-point temperature, for humid air, is the temperature at which water vapour
condensation (or desublimation) first occurs, at the same pressure and humidity content
(humidity ratio), when cooling a given sample of air. Mathematically it may be expressed as
[25]
In some processes, particularly those involving precipitation from the air, either liquid or solid water, it is
more practical to use the concept of Degree of Saturation , defined as the ratio of the actual water vapour content
in the air (all water in whatever form) to the water vapour content at saturation at the same temperature and total
pressure. Mathematically,
0 ! 4. At pressures near atmospheric and temperatures below ~ 25 C, n and are practically undistinguishable
for # 1.
for dry air (n = 0.0), the dew appears not any more as water but as liquid air. The dew point
temperature has then to be determined from the dew line equation for air. A six parameter
equation of the Saul & Wagner (1987) type is used for this purpose. This is an equation giving
the saturation pressure as function of the dew point temperature and has therefore to be solved
iteratively. The Newton-Raphson method is the most appropriate for this purpose. For pressures
higher than the critical pressure of air (37.85 bar) the dew first appears when crossing the critical
temperature line, which then represents the dew point temperature. The equation for the dew line
pressure is
[26]
The same form of the equation also applies for the bubble line. Although it is not required
here, the respective parameters are given below as well for the sake of completeness.
Pcr,air [bar] =
37.8502
Tcr,air [K ] =
132.62
ADEW
ABUBBLE
-6.756 572 06
-4.887 365 24
2.413 371 88
-1.880 307 58
-2.747 563 26
30.318 692 63
-8.134 449 89
-59.896 274 34
10.967 841 77
31.064 562 46
-12.233 885 33
6.173 064 75
Equation [25] above must be solved iteratively, and an algorithm for its solution is
described by the flow diagram depicted in Fig. 1.
The enthalpy of the saturated condensed phase is, for solid water (Hyland and Wexler
1983)
[28]
with
i
-0.647595x103
0.274292
0.2910583x10-2
0.1083437x10-5
0.107x10-5
Psv,s(T) is the saturation pressure of water vapour over solid water already defined.
For saturated liquid water (Hyland and Wexler 1983) the enthalpy is
[29]
-0.11411380x104
-0.1141837121x104
0.41930463x101
0.4194325677x101
-0.8134865x10-4
-0.6908894163x10-4
0.1451133x10-6
0.105555302x10-6
-0.1005230x10-9
-0.7111382234x10-10
-0.563473
0.6059x10-6
-0.036
and
[33]
vL has been defined before for the condensed phase (liquid), and the derivative of the
saturation pressure is easy to obtain from the equations given before.
For T = 273.16 K, becomes = 0.01214 kJ/kg, and hL is then
[34]
The thermodynamic wet-bulb temperature equation must be solved iteratively. The flow
diagram for an algorithm that solves it is depicted in Fig. 2.
The ranges of validity of the equations are also summarized at the end of this section.
[35]
Px,y stands for a generalized property of the component y, and the Xx stands for the molar
concentrations of the component x in the mixture. The Gi,j and Gj,i are functions of the viscosity
of the components in the mixture, calculated according to Wilke (1950).
[36]
[37]
The molar concentrations of dry air and water vapour, respectively Xa and Xw are related
to the humidity ratio, (kg H2O per kg dry air) as
[38]
Dry Air
-0.35376x10-2
-0.97494x10-6
0.669881x10-3
0.143387x10-5
0.654755x10-4
0.359061x10-7
0.942482x10-4
0.656244x10-7
0.174460x10-7
0.241612x10-12
-0.327450x10-7
-0.29905x10-10
[41]
with p in [Pa].
[42]
where v is the specific volume of humid air, related to the mass of dry air.
Input
Output
n
TDB
TWB
TDP
TDB
13
14
15
16
17
18
TDB
TWB
21
24
25
26
27
28
TDB
TDP
31
33
35
36
37
38
TDB
41
43
44
45
47
48
TDB
51
53
54
56
57
58
61
62
63
64
67
68
72
73
74
76
77
78
The transport properties are, in general, calculated from directly addressed functions.
Properties of Water
The properties of water required in the simulation of components, equipments and plants
for HVAC applications include properties for the liquid and solid phases, and the enthalpies of
condensation and sublimation. The properties of solid water are not for ice, but for frost, which
in its process of deposition onto metallic or other surfaces, has properties that vary with density
and temperature. The density of frost depends on the time since the start and on the intensity of
the mass transfer process. Since most simulation tools do not describe this time dependency, the
properties of frost are estimated values where the density is given an average value, and the other
properties are considered functions of the temperature at that density. The equations are
polynomials of the third degree, or less, adjusted to data in the literature. Their general form is
[43]
Property
Px,0
Px,1
Px,2
Px,3
0.123946x102
-0.732089x10-3
0.215735x10-3
-0.209977x10-6
Liquid H2O
-0.49803
0.595589x10-2
-0.750x10-5
0.0
Liquid H2O
0.116511
-0.100390x10-2
0.290714x10-5
-0.28193x10-8
Pr Liquid H2O
0.997904x103
-0.866620x101
0.252416x10-1
0.245920x10-4
Liquid H2O
-0.435062x101
0.903614x101
-0.259728x10-1
0.232507x10-4
h Sublimation
0.265139x104
0.186735x101
-0.389780x10-2
0.0
h Condensation
0.314712x104
-0.23660x101
0.0
0.0
Frost
0.250x103
0.0
0.0
0.0
Frost
0.12020x10-4
0.9630
0.0
0.0
Cp Liquid H2O
The units are SI units except for the enthalpies and specific thermal capacities where kJ/kg
and kJ/kg K are used, respectively.
References
Black, C. 1986. Importance of Thermophysical Data in Process Simulation, Int. J. Thermophysics, 7(4), 987-1002.
Cheung, H. L., A. Bromley, C. R. Wilke 1962. Thermal Conductivity of Gas Mixtures, AIChE Journal, 8(2), 221.
Flik, M. I., M. R. Conde 1986. PSYCH1 - A Pascal Procedure for the Calculation of the Psychrometric Properties
of Mois Air, Internal Report, Energy Systems Laboratory, ETH Zurich.
Goff, J. A. 1949. Standardization of Thermodynamic Properties of Moist Air, ASHVE Transactions, 459-484.
Grassmann, P. 1983. Physikalische Grundlagen der Verfahrenstechnik, 3. Aufl., Salle, Frankfurt, S. 95.
Harrison, L. P. 1965. Fundamental Concepts and Definitions relating to Humidity, in Humidity and Moisture Measurement and Control in Science and Industry, Proc. Int. Symp. on Humidity and Moisture, Vol. 3 Fundamentals and Standards, 3-256, Reinhold, New York.
Himmelblau, D. M. 1960. Solubility of Inert Gases in Water 0 C to near the Critical Point of Water, J. Chem. Eng.
Data, 5(1), 10-15.
Hyland, R. W., A. Wexler 1973a. The Enhancement of Water Vapor in Carbon Dioxide - free air at 30, 40 and
50 C, J. Res. NBS, 77A(1), 115-131.
Hyland, R. W., A. Wexler 1973b. The Second Interaction (Cross) Virial Coefficient for Moist Air, J. Res. NBS,
77A(1), 133-147.
Hyland, R. W., A. Wexler 1983a. Formulations for the Thermodynamic Properties of Dry Air from 173.15 K to
473.15 K, and of Saturated Moist Air from 173.15 K to 372.15 K, at Pressures up to 5 Mpa, ASHRAE
Trans., 89/2, 520-535.
Hyland, R. W., A. Wexler 1983b. Formulations of the Thermodynamic Properties of the Saturated Phases of H2O
from 173.15 K to 473.15 K, ASHRAE Trans., 89/2, 500-519.
Kell, G. S. 1975. Density, Thermal Expansivity, and Compressibility of Liquid Water from 0 C to 150 C:
Correlations and Tables for Atmospheric Pressure and Saturation, Reviewed and Expressed on the 1968
Temperature Scale, J. Chem. Eng. Data, 20(1), 97-105.
Leadbetter, A. J. 1965. The Thermodynamic and Vibrational properties of H2O and D2O Ice, Proc. Roy. Soc.,
A287, 403.
Mason, E. A., L. Monchick 1963. Survey of the Equations of State and Transport Properties of Moist Gases,
Humidity and Moisture - Measurement and Control in Science and Industry, Int. Symp. Humidity and
Moisture, Vol. 3 - Fundamentals and Standards, 257-272, Reinhold, New York.
Mason, E. A., S. C. Saxena 1958. Approximate Formula for the Thermal Conductivity of Gas Mixtures, The
Physics of Fluids, 1(5), 361-369.
Saul, A., W. Wagner 1987. International Equations for the Saturation Properties of Ordinary Water Substance, J.
Phys. Chem. Ref. Data, 16(4), 893-901.
Rossi, K. 1953. Die Diffusion von Wasserdampf in Luft bei Temperaturen bis 300 C, Forsch. Ing.Wesen, 19, 4958.
Wilke, C. R. 1950. A Viscosity Equation for Gas Mixtures, J. Chem. Phys., 18, 517.